Esters of polyoxyalkylene glycols and mixed dibasic acids as fiber finishes

ABSTRACT

Ester lubricant compositions are provided which provide a good balance of lubricity and emulsifiability. The esters are derived from polyoxyalkylene glycols with a dibasic acid mixture consisting of dimer acids and short-chain dibasic acids. The emulsions and clear, homogeneous lubricant solutions provide excellent spin finishes for fibers such as polyamides and polyesters.

- United States Patent [191 Sturwold et a1.

[11] 3,850,682 Nov. 26, 1974 1 ESTERS OF POLYOXYALKYLENE GLYCOLS ANDMIXED DIBASIC ACIDS AS FIBER FINISHES [75] Inventors: Robert J.Sturwold; Fred 0. Barrett, V

both of Cincinnati, Ohio [73] Assignee: Emery Industries, Inc.,Cincinnati,

Ohio

[22] Filed: June 7, 1972 [2]] Appl. No.: 260,516

Related US. Application Data [63] Continuation-in-part of Ser. No.223,752, Feb. 4,

1972, Pat. N0. 3,769,215.

[52] US. Cl ll7/138.8 F, 117/1385 F, 252/86,

252/495, 252/56 S, 260/75 T, 260/485 G [51] Int. Cl D06m 13/20, C08g17/14 [58] Field of Search 252/56 S, 49.3, 49.5, 8.6;

260/485 G, 75 R, 75 T; 57/164; 117/1388 F,

[56] References Cited UNITED STATES PATENTS 3,575,856 4/1971 Anton252/89 3,694,257 9/1972 Dumont 117/1395 F 3,769,215 10/1973 Sturwold eta1 252/495 OTHER PUBLICATIONS Ludewig, Polyester Fibers Chemistry andTechnology, Wiley-lnterscience (1964), pg. 195.

Kirk-Othmer, Encyclopedia of Chemical Technology, John Wiley & Sons,Inc., Vol. 12 (1967), pp. 579 & 580.

Primary Examiner-Melvin Goldstein Assistant Examiner-W. C. DanisonAttorney, Agent, or Firm-J. D. Rice; G. ApBaracka 57 ABSTRACT 5 Claims,No Drawings EST ERS OF POLYOXYALKYLENE GLYCOLS AND MIXED DIBASIC ACIDSAS FIBER FINISHES CROSS-REFERENCES This is a continuation-in-part ofcopending application Ser. No. 223,752 filed Feb. 4, 1972, now US. Pat.No. 3,769,215.

BACKGROUND OF THE INVENTION some of these are useful in aqueous systems.Many of the synthetic lubricants, however, are not readily emulsifiablewith water and if an emulsion can be formed, with or without the use ofadditional additives, most of these emulsions begin to separate after avery short time.

Synthetic lubricants derived from dimer acids such as obtained by thedimerization of oleic acid, linoleic acid or the like have beendescribed in US. Pat. Nos. 2,767,144 and 3,233,635. While extremelyeffective lubricants for a variety of applications such as metal workingand spin finishing of fibers can be obtained through the use of dimeracids, the compatibility of the dimer-based lubricant with water isgenerally very poor. A dimer-based synthetic polyester lubricant havingincreased hydrophilic character and useful in aqueous systems isdisclosed in US. Pat. No. 3,492,232. The polyester is derived from thereaction of 0.8 to 2.0 mols, and more preferably 1.0 to 1.5 mols,polyoxyalkylene glycol having a degree of polymerization of 4 to 200 and1 mol of a dimer of C to C fatty acid. While the composition of the Pat.No. 3,492,232 present a significant advance in the technology ofdimer-based lubricants they are not without certain disadvantages. Theresulting aqueous emulsions are relatively unstable and undergo partialphase separation within a very short period. Furthermore, many of thepolyesters cannot be satisfactorily emulsified without the use ofadditional emulsifying agents of the cationic and nonionic types.Employing additional emulsifier increases the cost of the lubricantcomposition in addition to adding another process variable and istherefore undesirable. The stability of the emulsions can be improvedthrough the use of higher molecular weight polyoxyalkylene glycols withthe dimer, but while the use of these high molecular weightpolyoxyalkylene glycols improves the physical characteristics of theemulsion it severely re-' duces the lubricating efficiency of thecomposition since the weight percent dimer acid incorporated therein isproportionately decreased.

It would be highly advantageous to have dimer acidderived syntheticlubricants which are readily emulsifiable with water. It would beespecially advantageous if stable emulsions could be formed without theuse of external emulsifying aids and simply by moderately agitating thesyntheticlubricant with cold tap water. Additional benefit would bederived if synthetic lubricants employing low molecular weightpolyoxyalkylene glycols with dimer acid could be prepared so that a highweight percent dimer acid could be obtained; if these lubricants werereadily emulsifiable without the use of external emulsifying agents; andif the resulting emulsions were stable.

SUMMARY OF THE INVENTION We have now discovered that improved esterlubricant compositions derived from dimer acid and polyoxyalkyleneglycols are obtained by incorporating therein an amount of short-chaindibasic acid. The ester mixtures of this invention are more readilyemulsifiable with water than polyesters derived from polyoxyalkyleneglycol and dimer acidl alone. Stable emulsions are obtained with thelubricant compositions of this invention without the use of externalemulsifying aids. Quite unexpectedly it has been found that theincorporation of the short-chain dibasic acid permits the use of lowmolecular weight polyoxyalkylene glycols with the dimer acid and thatthe resulting mixed ester compositions, in addition to having increasedlubricity as a result of the high weight percent dimer acid present,also have superior emulsificationproperties. This invention providessynthetic ester lubricants which have a good balance of emulsificationand lubrication properties. A further advantage and completelyunexpected result is the discovery that clear, homogeneous lubricantsolutions can be prepared when the molar ratio of the polyoxyalkyleneglycol, dimer acid and short-chain dibasic acid is within certaindefined limits.

The ester lubricants of the present invention are obtained by thecondensation reaction of polyoxyalkylene glycols having molecularweights ranging from 300 to 4000 and more preferably in the range 400 to1000, a dimer acid containing from about 32 to 54 carbon .atoms and ashort-chain dibasic acid containing from 2 to 12 carbon atoms and morepreferably from about 6 to 10 carbon atoms. The molar ratio of dibasicacids (dimer acid plus short-chain dibasic acid) to polyoxyalkyleneglycol will be 1:1.5 2.1. The dimer acid will constitute from about 95to 5 mol percent of the total dibasic acid while the short-chain dibasicacid will range from about 5 to 95 mol percent. Excellent results areobtained when about to 20 mol percent of the total dibasic acid isshort-chain dibasic acid. To obtain water-soluble ester lubricants about7.5 to about 20% by weight short-chain dibasic acid, based on theoverall ester composition, is employed. The water-soluble ester productshave acid values of about 15 or below. The concentration of the ester inaqueous emulsions or solutions useful as lubricants will generally rangefrom about 0.1 to 25% by weight of the lubricant composition.

DETAILED DESCRIPTION The ester lubricants of this inventionare-condensation products of polyoxyalkylene glycols with a mixture ofdibasic acids and shortchain dibasic acids. These ester compositions areuseful as lubricants and are readily emulsifiable with water without theaddition of external emulsifying agents.

To obtain the lubricant esters of this invention, a polyoxyalkyleneglycol having a molecular weight from about 300 to about 4000, and morepreferably from 400 to 1000, is employed. The recurring alkylene groupsmay contain 2 to 4 carbons atoms anduseful polyoxyalkylene glycolshaving varying degrees of polymerization include: polyethylene glycols,polypropyl ene glycols, polybutylene glycols, poly(ethylenepropylene)glycols and the like. Polyethylene glycols having molecular weights from400 to about 1000 are especially useful and are available fromcommercial suppliers under the trade designations Carbowax" and Polyoxor they may be synthesized in the conventional manner. The molecularweights recited above indicate the average molecular weight of thepolyoxyalkylene glycol and it is understood that these compositions aremixtures of polyoxyalkylene glycols having widely divergent molecularweights. Polyoxyalkylene glycols having molecular weights less thanabout 300 or greater than about 4000 should not, however, be present insignificant amounts.

Condensed with the polyoxyalkylene glycol is a mixture of dibasic acidsconsisting of dimer acid and shortchain dibasic acid. The molar ratio ofthe dibasic acids, including both the dimer acid and the short-chaindibasic acid, to the polyoxyalkylene glycol will range from about1:5.5-2.l with exceptional results being obtained when the molar ratiois 1:l.75-2.0. The proportion of dimer and short-chain dibasic acids maybe widely varied.

Useful dimer acids for the compositions of this invention contain fromabout 32 to 54 carbon atoms. The dibasic acids may be obtained byprocesses known to the art, however, they are most frequently obtainedby the polymerization of monocarboxylic acids containing ethyleneicunsaturation. The monocarboxylic unsaturated acids generally containfrom about 16 to 26 carbon atoms and include, for example, oleic acid,linoleic acid, eleostearic acid and similar singly or doubly unsaturatedacids. To obtain the preferred dimer acids 2 mols of the unsaturatedmonocarboxylic acid are reacted, i.e., dimerized. If the resulting dimeracid contains ethyleneic unsaturation it may be beneficial tohydrogenate it to obtain the saturated material prior to reaction withthe polyoxyalkylene glycol. Mixtures of dimer acids may be employed.Trimer and tetramer acids may also be present with the dimer acid and donot adversely affect the lubricant properties of the resulting estercompositions so long as about 50% by weight of the mixture arepolymerized acids. Commercially available compositions sold under thetrademark Empol, mixtures of polymerized fatty acids with dimer acid asthe major constituent, may be advantageously employed. Especially usefulare mixed acid products which will contain 75 weight percent or moredimer acid with the remainder being unpolymerized fatty acids or morehighly polymerized acids such as trimer acids.

The short-chain dibasic acids contain from 2 to about 12 carbon atoms.Short-chain dibasic acids containing 6-l0 carbon atoms are especiallypreferred for the present invention. Typical short-chain dibasic acidsinclude oxalic acid, malonic acid, succinic acid, glutaric acid, adipicacid, azelaic acid, sebacic acid, dodecanedioic acid and the like.Mixtures of one or more short-chain dibasic acids may be used.

The dibasic acid mixture consists of about 95 to mol percent dimer acidswith about 5 to 95 mol percent of one or more short-chain dibasic acids.Preferred ester lubricant compositions contain from about 80 to 10 molpercent short-chain dibasic acid and from 90 to mol percent of thedimer.

The condensation of the polyoxyalkylene glycol with the dimer andshort-chain dibasic acids is conducted employing conventionalesterification techniques, that is, by heating the reaction mixture withor without a catalyst at a temperature from about 100 to 300C whileremoving the water of reaction. The reactions are most generallyconducted over the temperature range 175 to 250C. It is not necessarythat a catalyst be employed for the esterification reaction, however,conventional acid catalysts such as sulfuric acid, alkyl and arylsulfonic acids such as p-toluene sulfonic acid, phosphorous acids or thelike may be employed. The reaction may be carried out in a diluent whichis inert to the reaction conditions employed and which, preferably, willform an azeotrope with water to facilitate the removal of the water ofreaction. The amount of reactants employed is in accordance with themolar ratios set forth above. For preparation of suitable esterlubricants it is undesirable for the esterification reaction to be lessthan about complete, that is, 70% or more of the carboxyl groups shouldbe reacted. The reaction is more generally continued to approximatelycompletion. This may be detennined by measurement of the acid value orhydroxyl value or by measuring the amount of water evolved. For thepreparation of certain preferred ester lubricants which arewater-soluble it is preferred that the reaction be continued until it iscomplete or even higher or, in terms of acid value, the reaction mixturehas an acid value of about 15 or below.

As an alternative procedure for the preparation of the present esterlubricants, the dimer and short-chain dibasic acid may be reacted in thepresence of ethylene oxide. In this way the polyoxyethylene glycol wouldbe prepared in situ. Suitable catalysts and diluents could be added. Itis generally found, however, that more uniform control of molecularweight of the products it obtained when the polyoxyethylene glycol isseparately prepared.

Small amounts of other compounds capable of entering into the reactionmay also be included with the polyoxyalkylene glycol, dimer andshort-chain dibasic acid and are within the scope of the presentinvention. Aromatic dibasic acids, diols and polyols, diamines andpolyamines may be employed in amounts which do not detract from theemulsification and lubrication properties to modify the resultinglubricant composition. For example, the use of diamines, such asdimethylaminopropylamine, may be desirable to enhance the anticorrosionproperties of the ester if it is to be used as a metalworking lubricant.The amount of these materials will not exceed about 10% and morepreferably 5% by weight of the overall ester composition.

The esters of the present invention provide a convenient means to obtaina good balance of lubrication and emulsification properties which wasnot previously possible when polyoxyalkylene glycols were simply reactedwith dimer acids without the addition of short-chain dibasic acids. Toachieve good lubrication properties with the prior art polyesters wouldrequire that the emulsification properties be compromised. Even ifadditional external emulsifying aids were added, the resulting emulsionswere not always completely satisfactory and in most instances they wouldbegin to separate after a very short time. Acceptable emulsions can beproduced employing the teachings of the prior art if the amount of dimeracid is diminished, however, this results in a marked decrease in thelubrication properties. For example, a polyester prepared by thecondensation of dimer acid with a polyethylene glycol of molecularweight 2000 or greater in accordance with prior art procedure would forman acceptable emulsion, but the would not emulsify readily or theemulsion, if formed,

would not be stable.

In accordance with the present invention we have prepared mixed esterlubricants which are, at the same time, readily emulsifiable andexcellent lubricants. This is accomplished by replacing a portion of thedimer acid with a short-chain dibasic acid. In this way lower molecularweight polyoxyalkylene glycols can be employed without reducing thehydrophilic character of the resulting ester and emulsifiability iscomparable or superior to compositions containing much largerproportions of the hydrophilic moiety. Also by the use of low molecularweight polyoxyalkylene glycols, the weight percent of the dimer acidpresent in the resulting ester mixture may be proportionately increasedwith the result that the lubricity of the ester compositions is markedlyenhanced. Thus, the present ester lubricant compositions provide theproper balance of dimer (which contributes to the lubricity) andpolyoxyalkylene glycol which contributes to the emulsifiability) so thatexceptionally useful products are obtained. When very high molecularweight polyoxyalkylene glycols are reacted with dimeracid in the absenceof a short-chain dibasicacid the lubrication properties of the resultingester products are impaired. Similarly, when very low molecularweightpolyoxyalkylene glycols are employed the emulsifiability is poorand the product unacceptable.

While the ability of the present invention to provide ester compositionshaving excellent lubricating and emulsifying properties is in itselfvery useful, a preferred embodiment of this invention is even moreadvantageous since it provides completely water-soluble esterlubricants. The water solutions are clear and homo geneous in allproportions. To obtain the watersoluble ester compositions the lubricantester will contain from about 7.5 to about by weight of the shortchaindibasic acid and have an acid value of about 15 or below. Acid valuesabove about 15 are unacceptable if clear solutions are to be obtained.It is unexpected that as the acid value of the ester composition isdecreased the water solubility or hydrophilic character of the esters isincreased. The solutions produced in accordance with this preferredembodiment are stable I and do not discolor or become cloudy uponstanding.

The esters have excellent lubricity in addition to being completelywater-soluble and may be successfully used in various metal workingoperations and as fiber finishes.

The lubricants of this invention are useful for working metals asaqueous emulsions or as the clear aqueous solutions. The concentrationof the ester for this purpose will generally range from about 0.1 toabout by weight of the emulsion or solution although these esters mixwith water in all proportions. The lubricant formulations may be addedto the metal-working elements or the metal itself by spraying or withother similar equipment and form a uniform continuous film between therolls and the metal, thereby reducing friction and heat buildup. Theselubricants are useful for working both ferrous and nonferrous metals andthey may be formulated with other additives such as stabilizers,corrosion inhibitors and the like depending on the enduse application.

The present ester compositions are also useful as an overfinish forpolymeric fibers derived from materials such as polyolefins, polyamides,polyacrylonitriles and polyesters. Such finishes are required duringtheprocessing of the fibers into yarns and fabrics to increase thesurface lubricity thereby reducing fiber-fiber friction and frictionbetween the fiber andguides, 'draw pins, etc., of the processingequipment. Use of these finishing agents minimizes damage to the fibers,decrease filament breakage and facilitate the various processing steps.The ester compositions of this invention also reduce static chargebuildup in the fibers during the processing. The esters of thisinvention are especially useful with polyesters and polyamides and theysignificantly improve the lubricity of the fibers and improve theresistance to static electrical charge buildup.

Polyesters for which the present compounds, particularly the poly(ethylene glycol) dlimerates, are useful include any of thecondensation. polymers obtained when one or more diols are reacted withone or more dibasic acids or suitable derivatives thereof. They are alsouseful with copolyesters and. modified copolyesters. Glycols from whichuseful polyesters are obtained generally have the formula wherein n isan integer from about 2 to 10. Such glycols include ethylene glycol,1,3-propanediol, l,5- pentanediol, l,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol and the like. Dicarboxylicacids typically employed include terephthalic acid, isophthalic acid,adipic acid, sebacic acid, succinic acid, oxalic acid, glutaric acid,pimelic acid, suberic acid, azelaic acid, and the like. In addition tothese more common diols and dicarboxylic acids other useful reactantsmight include glycerol, sorbitol, pentaerythritol, methoxypolyethyleneglycol, neopentyl glycol monohydroxypivalate, trimethylol propane,trimesic acid, p,p'-dicarboxydiphenylmethane,p,p'dicarboxydiphenoxyethane, p-carboxyphenoxy acetic acid and the like.Especially useful polyesters for the purpose of the present inventionare poly(ethylene terephthalate) and poly( l,4-cyclohexylenedimethyleneterephthalate) because of their commercial availability and superiorfiber-forming characteristics.

The present compositions are also useful as spin finishes to lubricateand provide protection against static charge buildup with polyamidesformed by the reaction of dicarboxylic acids, such as described abovefor the preparation of polyesters, and a diamine or suitable derivativethereof. Diamines which may be employed have the general formula H N ouNH, wherein n is an integer from about 2 to 10, such as ethylenediamine,propylenedianrine, tetramethylenediamine, pentamethylenediamine,hexamethylenediamine, decamethylenediamine and the like. Nylon-6 andnylon-6,6, are especially useful for the present invention. Polyamidesderived from the reaction of certain amino acids such as 6-aminocaproicacid, 7- aminoheptanoic acid, or the lactams of these acids,

may also be treated in accordance with the present invention.

In general, the esters of this invention may be employed with anypolymeric material as a lubricant and to obtain improved resistivity tostatic electrical charge buildup. The emulsions or solutions of theesters can be applied to the polymer powder, on the surface of formedobjects such as pellets, rods, fibers, filaments, yarns, etc. Whenemployed as a fiber finish the concentration of the ester and the pickupare controlled to give the final weight of ester desired for acceptableprocessing. Finishes are typically applied to the fiber by passisng thefiber through a bath or over a saturated roll containing the emulsion orsolution or by directly spraying the fiber. The esters may be added topolyesters, polyamides or other fiber-forming polymers by themselves orin combination with other additives such as stabilizers, plasticizers,additional lubricants and antistatic agents and the like.

The esters may be incorporated into the polyester, polyamide or otherpolymeric material using conventional mixing equipment. They may beadded directly to the polymerizer while the polymer is being formed orreacted with a suitable prepolymer. The addition may be made at anystage of the polymerization, in toto, incremently or by proportioning,the manner and mode of addition being governed by the relativereactivities of the reactants and reaction conditions employed. Usingthis technique the ester becomes an integral part of the polymerstructure and consequently imparts some permanence to the lubricant andantistatic properties. The amount of ester reacted into the polymer willvary depending on the number of reactive groups available on the ester.As will be recognized by the person skilled inthe art, numerousvariations are possible depending on the particular end-use applicationand are within the scope of the present invention. Irrespective of themethod of treating the polymer with the ester to obtain the propertiesheretofore described, the ester will constitute from about 0.1 to l%,and more preferably from 0.2 to 2.5% by weight, of the polymercomposition.

The following examples illustrate this invention more fully, however,the examples are not intended to limit the scope of the invention. Allparts and percentages in the examples are given on a weight basis unlessotherwise stated.

EXAMPLE I To a glass reactor equipped with a stirrer, thermometer andwater trap were charged 1030 grams (0.9 equivalent ratio) of dimer acid(Empol 1018 containing 83% C dibasic acid), 37.6 grams (0.1 equivalentratio) azelaic acid and 1600 grams (2.0 equivalents ratio) polyethyleneglycol having an average molecular weight of 400. The reaction mixturewas heated with stirring to about 200C and held for approximately 4hours during which time 5 l mls of water were removed. A vacuum of aboutI torr was pulled on the system to remove additional water of reaction.After one hour the reaction mixture was sampled and had an acid value ofabout 15.5. Heating was continued under vacuum for four more hoursbefore the reaction mixture was cooled and poured up. The resultinglubricant ester composition had a final acid value of 6.7, hydroxylvalue of 93.1, viscosities (ASTM D 445-65) at 100F and 210F of 548 esand 70.4 cs, respectively, and flash and fire points (ASTM D 92-66) of555F and 605F, respectively.

A portion (20 mls) of the ester composition was poured into mls of coldtap water while stirring with a glass rod. An emulsion was immediatelyobtained. This emulsion was stable and showed no signs of phaseseparation after standing 48 hours at room temperature. Even after aweeks time the emulsion appeared homogeneous. A sample preparedidentically but with the azelaic acid excluded from the mixture was onlydifficulty emulsifiable. To obtain an emulsion required vigorousagitation with a mechanical stirrer. When this emulsion was allowed tostand at room temperature there was appreciable phase separation afteronly 24 hours with significant amounts of the oil settling to the bottomof the beaker.

To demonstrate the effectiveness of the ester compositions of thisinvention as lubricants they were evaluated with a Falex machine. Thismachine provides a convenient and reliable means to determine the filmstrength or load-carrying properties of materials as extreme pressuresare applied. Falex testing is recognized throughout the industry as ameans of measuring the relative effectiveness of various lubricants. TheFalex wear test (ASTM D 2670-67) employs a 60 gram sample when thestraight ester is being evaluated. A 600 gram sample is used whenaqueous emulsions or solutions of the ester are to be tested. Theloading device is attached and the cup containing the sample beingevaluated positioned so that the steel pin and blocks are completelyimmersed in the sample. The load is then increased to 350 lbs and runfor 5 minutes. After this time the load is further increased to 1000 lbsand maintained for 30 minutes when testing straight oils or one hourwhen evaluating lubricant emulsions or solutions. Readings are taken atthe beginning of the hour, after thirty minutes, and at the end of thehour and the difference in the readings indicates the amount of wear.

Three samples of the lubricant ester composition of this example wereevaluated in accordance with the described test procedure. The straightoil was evaluated and also 10% and 5% aqueous emulsions were tested.Test results obtained are as follows:

SAMPLE UNITS WEAR Straight ester: after 30 minutes 18 after 60 minutes30 10% aqueous emulsion: after 30 minutes 154 5% aqueous emulsion: after30 minutes 174 EXAMPLE II Employing identical reactants and a similarprocedure to that described in Example I, 715 grams (0.5 equivalentratio) dimer acid, 235 grams (0.5 equivalent ratio) azelaic acid and2000 grams (2.0 equivalents) polyethylene glycol were heated at 200C for6 hours 200F of 36.6 cs, and flash and fire points of 530 and 585F,respectively. The ester readily dissolved in water in all propertions.No cloudiness was observed the resulting solutions were clear andhomogeneous;

Falex wear tests gave the following results:

A water-soluble ester lubricant containing about-8% by weight adipicacid was obtained from the reaction of 0.4 equivalent dimer acid (83% Cdibasic acid), 0.6 equivalent adipic acid and 2.0 equivalentspolyethylene glycol having a molecular weight of 400. The reaction wascontinued until an acid value of 10.3 was achieved. The resulting estercomposition had a viscosity of 163 I cs at 100F. The ester lubricantmixed with water in all proportions to give clear solutions. Watersolutions containing 10% and 5% of the so-prepared ester were evaluatedin the Falex test machine and showed only 132 and 156 units of wear,respectively, after 30 minutes testing at 10.00 psi.

Repeating the above example using 0.5 equivalent dimer acid and 0.5equivalent adipic acid and running the reaction to an acid value of 12.9gave useful ester lubricants. These compositions when mixed with waterdid not give clear solutions but did formstable emulsions without theuse of external emulsifying aids. The emulsions had excellent shelflives and were effective lubricants.

.EXAMPLE 1V When Example I was repeated using 0.7 equivalent dimer acid,0.3 equivalent azelaic acid and 2.0 equivalents polyethylene glycol, auseful ester lubricant composition having an acid value of 9.1 wasobtained. The ester had a viscosity of 425 cs at 100F and was readilyemulsifiable in cold tap water with minimal stirring and withoutaddition of external emulsifying aids. The emulsion so-produced hadexcellent shelf life and was an efficient lubricant. A 5% aqueousemulsion of this ester gave less than 150 units wear in the Falexmachine after 30 minutes at 1000 psi.

Ester lubricant compositions were also prepared which incorporated up to0.2 equivalent of an amine corrosion inhibitor such as diethanolamine ordimethylaminepropylamine. The presence of these amines significantlyimproved the corrosion properties of the lubricant composition withoutadversely affecting the emulsion and lubrication characteristics. Insome instances the amines enhance the emulsion properties of the estercomposition even at reduced polyethylene glycol levels.

EXAMPLE V Example I was repeated using 0.8 equivalent dimer acid, 0.2equivalent azelaic acid and 2 equivalents polyethylene glycol. Thelubricant ester (acid value 15.5) was easily emulsified. Stableemulsions were obtained which were useful cutting oils when used with atungsten carbide bit.

EXAMPLE VI To demonstrate the ability of the present esters to functionas fiber/metal lubricants and improve the resistance of theso-lubricated fibers to static charge buildup several of the esterproducts were applied as finishes to polyester yarn and compared againsta commercially available product used by the industry as a component fortextile finishes. Three samples (A-C) were prepared and applied at 0.5%o.w.f. on 150 denier polyester yarn which had been solvent-stripped toremove any finish applied by the producer. Samples A and B contained theesters of Examples I and II, respectively, while Sample C was preparedwith Emerest 2650 a product of Emery Industries, Inc., identified aspolyethylene glycol 400 monolaurate. The finishes were all applied fromaqueous systems with an Atlab Finish Applicator and the treated fibersthen conditioned for 24 hours at F and 65% relative humidity prior totesting. Frictional properties were measured with a Rothschild F-Meterwith the initial tension held constant at 10 grams, a yarn speed ofM/minute and yam/- metal contact angle of Test results are reportedbelow. Antistatic properties were also determined by insulating one ofthe pulleys on the F-meter and connecting it to a voltmeter andmeasuring the static charge produced on the pulley after an 8-seconclinterval. The voltage buildup is reported in the table below. A staticmeasurement for antistatic properties was made by placing a 100 voltcharge on a strand of the yarn connected to a ground and determining'thetime required for the charge to dissipate to 50 volts. This data isreported in the table below under the column headed Bleed-off.

Sample t (g) f Buildup (V) Bleed-off (See) A 37 0.39 s00 30 B 30 0.32350 10 C 22 0.22 625 12 EXAMPLE VII Single strand nylon (Dupont 158417)was immersed in 0.5% water emulsion/solution of the following:

Sample Additive A Product of Example I B Product of Example ll Thefibers were then conditioned at 68F and 40% relative humidity and testedusing the static bleed-off test. Results were as follows: dimerhydrocarbon acids containing 32 to 54 carbon atoms and 95 to not percentshort-chain dibasic hydrocarbon Fiber treated with Minutes to 50%Bleed-off about 300 to about 4000 and recurring alkylene groups,containing from 2 to 4 carbon atoms with one mol of a mixture ofdibasic acids consisting of 5 to 95 mol percent short-chain dibasichydrocarbon acids containing 2 to 12 carbon atoms, said ester having ormore of the carboxyl groups reacted.

2. The lubricated fiber of claim 1 wherein the polyoxyalkylene glycol isa polyethylene glycol of molecular weight 400 to 1000 and the dibasicacid mixture contains from 20 to 90 mol percent short-chain dibasichydrocarbon acid containing 6 to 10 carbon atoms.

3. The lubricated fiber of claim 2 wherein the mol ratio of dibasicacids to polyoxyethylene glycol is l:l.752.0 and greater than of thecarboxyl groups of the dibasic acids are reacted.

4. The lubricated fiber of claim 3 wherein the acid value of the esteris 15 or below and the short-chain dibasic hydrocarbon acid comprisesfrom about 7.5 to 20 weight percent of the ester composition.

5. The lubricated fiber of claim 4 wherein the shortchain dibasichydrocarbon acid is azelaic acid and the polyester is poly(ethyleneterephthalate) or poly( 1,4-

cyclohexylenedimethylene terephthalate).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,850,682 Dated November 26, 1975 lnv fl Robert J. Sturwold et al It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 12, 1ine 4, after "cent" should be inserted dimer hydrocarbonacids containing 32 to 54 carbon atoms and 95 to 5 mol percent Signedand Sealed this I Twelfth D f October 1976 [SEAL] Arrest:

RUTH C. MSON C. MARSHALL DANN Arresting Officer (ommissiuner uflatentsand Trademarks

1. A LUBRICATED FIBER COMPRISING A POLYESTER HAVING DEPOSITED THEREONABOUT 0.1 TO 10% BY WEIGHT OF AN ESTER OBTAINED BY THE REACTION OF 1.5TO 2.1 MOLS POLYOXYETHYLENE GLYCOL HAVING A MOLECULAR WEIGHT FROM ABOUT300 TO ABOUT 4000 AND RECURRING ALKYLENE GROUPS CONTAINING FROM 2 TO 4CARBON ATOMS WITH ONE MOL OF A MIXTURE OF DIBASIC ACIDS CONSISTING OF 5TO 95 MOL PERCENT SHORT-CHAIN DIBASIC HYDROCARBON ACIDS CONTAINING 2 TO12 CARBON ATOMS, SAID ESTER HAVING 70% OR MORE OF THE CARBOXYL GROUPSREACTED.
 2. The lubricated fiber of claim 1 wherein the polyoxyalkyleneglycol is a polyethylene glycol of molecular weight 400 to 1000 and thedibasic acid mixture contains from 20 to 90 mol percent short-chaindibasic hydrocarbon acid containing 6 to 10 carbon atoms.
 3. Thelubricated fiber of claim 2 wherein the mol ratio of dibasic acids topolyoxyethylene glycol is 1:1.75-2.0 and greater than 85% of thecarboxyl groups of the dibasic acids are reacted.
 4. The lubricatedfiber of claim 3 wherein the acid value of the ester is 15 or below andthe short-chain dibasic hydrocarbon acid comprises from about 7.5 to 20weight percent of the ester composition.
 5. The lubricated fiber ofclaim 4 wherein the short-chain dibasic hydrocarbon acid is azelaic acidand the polyester is poly(ethylene terephthalate) orpoly(1,4-cyclohexylenedimethylene terephthalate).